EP0754721B1 - Composition d'élastomère contenant du fluor - Google Patents

Composition d'élastomère contenant du fluor Download PDF

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Publication number
EP0754721B1
EP0754721B1 EP96111051A EP96111051A EP0754721B1 EP 0754721 B1 EP0754721 B1 EP 0754721B1 EP 96111051 A EP96111051 A EP 96111051A EP 96111051 A EP96111051 A EP 96111051A EP 0754721 B1 EP0754721 B1 EP 0754721B1
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EP
European Patent Office
Prior art keywords
fluorine
containing elastomer
elastomer composition
bisamidrazone
perfluoro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96111051A
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German (de)
English (en)
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EP0754721A3 (fr
EP0754721A2 (fr
Inventor
Satoru Saito
Haruyoshi Tatsu
Sergei Vasil'evich Sokolov
Alexandre Nikolaevich Kollar
Sergei Rafailovich Sterlin
Yurii Vilovich Zeifman
Sergei Anatol'evich Postovoi
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Nippon Mektron KK
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Nippon Mektron KK
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Publication of EP0754721A3 publication Critical patent/EP0754721A3/fr
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Publication of EP0754721B1 publication Critical patent/EP0754721B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds

Definitions

  • the present invention relates to a fluorine-containing elastomer composition, and more particularly to a fluorine-containing elastomer composition, which comprises a fluorine-containing elastomer having a cyano group as a cross-linkable group and a new type of a vulcanizing agent.
  • a vulcanization product having good heat resistance and solvent resistance was successfully obtained by using a novel bisamidrazone represented by the following general formula as a vulcanizing agent for a fluorine-containing elastomer having a cyano group as a cross-linkable group: wherein R is an alkylidene group having 1 to 6 carbon atoms, preferably an isopropylidene group or a perfluoroalkylidene group having 1 to 10 carbon atoms, preferably a perfluoroisopropylidene group (Japanese Patent Application No.6-282943).
  • An object of the present invention is to provide a fluorine-containing elastomer composition, which comprises a fluorine-containing elastomer having a cyano group as a cross-linkable group and a bisamidrazone compound as a new type of curing agent and is capable of producing vulcanization products having desired physical properties and being freed from the problem of processability.
  • a fluorine-containing elastomer composition which comprises a fluorine-containing elastomer having a cyano group as a cross-linkable group and a bisamidrazone compound represented by the following general formula as a vulcanizing agent: wherein Rf is one of the following groups: (CF 2 )n, where n: 1 to 10, CFX(OCF 2 CFX)mO(CF 2 )n, where X: F or CF 3 ; n: 1 to 10, m: 1 to 2 and CFX(OCF 2 CFX)pO(CF 2 )nO(CFXCF 2 O)qCFX, where X: F or CF 3 ; n: 1 to 10 ; p+q: 8.
  • the bisamidrazone compound for use in the present invention can be readily prepared by reaction of the corresponding dinitrile compound with hydrazine hydrate [J. Am. Chem. Soc., vol.82, page 4700 (1960)].
  • the thus prepared bisamidrazone compound is used as a vulcanizing agent for the fluorine-containing elastomer having a cyano group as a cross-linkable group.
  • a terpolymer comprising about 45 to 75% by mole of tetrafluoroethylene, about 50 to about 25% by mole of perfluoro(lower alkyl vinyl ether) or perfluoro(lower alkoxy-lower alkyl vinyl ether) and about 0.1 to 5% by mole of a perfluoro unsaturated nitrile compound, the sum total being 100% by mole, is usually used as such a fluorine-containing elastomer.
  • perfluoro(lower alkyl vinyl ether) perfluoro(methyl vinyl ether) is usually used.
  • CF 2 CFO(CF 2 ) n OCF(CF 3 )CN (n: 2 to 5)
  • CF 2 CFO[OCF 2 CF(CF 3 )] n O(CF 2 ) m CN (n: 1 to 2, m: 1 to 6)
  • CF 2 CFO(CF 2 ) n CN (n: 1 to 8)
  • CF 2 CF[OCF 2 CF(CF 3 )] n OCF 2 CF(CF 3 )CN (n: 1 to 2)
  • the terpolymer comprising the foregoing components as essential can be further copolymerized with fluorinated olefins or various vinyl compounds to such a degree as not to inhibit the copolymerization reaction and impair the physical properties of vulcanization products (i.e. to not more than about 20% by mole).
  • Fluorinated olefins for use in the present invention include, for example, vinylidene fluoride, monofluoroethylene, trifluoroethylene, trifluoropropylene, pentafluoropropylene, hexafluoropropylene, hexafluoroisobutylene, chlorotrifluoroethylene, dichlorodifluoroethylene, etc.
  • Vinyl compounds for use in the present invention include, for example, ethylene, propylene, 1-butene, isobutylene, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, trifluorostyrene, etc.
  • the fluorine-containing elastomer composition comprising the foregoing components as essential can further contain appropriate ingredients, when required, for example, an inorganic filler such as carbon black, silica, etc.; an acid receptor such as divalent metal oxides or hydroxides including lead (II) oxide , zinc oxide, magnesium hydroxide, calcium hydroxide, etc., hydrotalcite, etc.; a pigments; a processing aidditive; a plasticizers, etc.
  • the composition can be prepared by kneading through rolls, a kneader, Bambury mixer, etc. The composition is cured by heating at a temperature of about 150 to about 220°C for about 5 to about 60 minutes in a compression molding machine, etc.
  • Post curing (secondary vulcanization) is carried out at a temperature of about 200 to about 320°C for about 10 to about 70 hours.
  • an inert gas atmosphere such as a nitrogen gas atmosphere, etc.
  • vulcanization products having not only good heat resistance and solvent resistance, but also considerably improved roll kneadability and processability during the vulcanization-molding can be obtained from a fluorine-containing elastomer having a cyano group as a cross-linkable group.
  • the minimum torque shows a low figure at the vulcanization.
  • the present fluorine-containing elastomer composition is effectively utilized as a material for vulcanization-molding of O-rings, sheets, etc. to be used under severe conditions.
  • the mixtures were each kneaded through a two-roll mill at a temperature of 40 to 45°C, and the resulting kneaded mixtures were then subjected to press vulcanization (primary vulcanization) at 180°C for 30 minutes and then to oven vulcanization (secondary vulcanization) in a nitrogen gas atmosphere under the following conditions:
  • Example 1 and 4 a terpolymer of tetrafluoroethylene-perfluoro(methyl vinyl ether)-perfluoro(3-oxa-8-cyano-1-octene) in a molar ratio of 68.8 : 30.0 : 1.2 (Copolymer B) was used in place of Copolymer A.
  • Example 1 using Copolymer A 0.7 parts by weight of bisamidrazone of 2,2-bis(4-carboxyphenyl)hexafluoropropane represented by the following formula was used in place of perfluoroadipic acid bisamidrazone obtained in Reference Example 1:
  • Example 5 using Copolymer B 0.5 parts by weight of bisamidrazone of 2,2-bis(4-carboxyphenyl)hexafluoropropane was used in place of perfluoroadipic acid bisamidrazone obtained in Reference Example 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (7)

  1. Composition élastomère contenant du fluor, qui comprend un élastomère contenant du fluor présentant un groupe cyano en tant que groupe réticulable, et un composé de bisamidrazone représenté par la formule générale suivante comme agent de vulcanisation:
    Figure 00170001
    dans laquelle Rf représente l'un des groupes suivants:
       (CF2)n, où n: 1 à 10,
       CFX(OCF2CFX)mO(CF2)n, où X: F ou CF3; n: 1 à 10; m: 1 à 2
       et
       CFX(OCF2CFX)pO(CF2)nO(CFXCF2O)qCFX, où X: F ou CF3; n: 1 à 10; p+q: 8.
  2. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle l'élastomère contenant du fluor présentant un groupe cyano en tant que groupe réticulable est un terpolymère comprenant- environ 45 à environ 75% en moles de tétrafluoroéthylène, environ 50 à environ 25% en moles de perfluoro(éther de vinyle et d'alkyle inférieur) ou perfluoro(éther de vinyle d'alcoxy inférieur-d'alkyle inférieur) et environ 0,1 à 5% en moles d'un composé nitrile insaturé perfluoré, le total faisant 100% en moles.
  3. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle le composé de bisamidrazone est
    Figure 00180001
  4. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle le composé de bisamidrazone est
    Figure 00180002
  5. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle le composé de bisamidrazone est NCCF(CF3)[OCF2CF(CF3)]nO(CF2)3O[CF(CF3)CF2O]mCF(CF3)CN où n + m = 5.
  6. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle on utilise environ 0,1 à environ 5 parties en poids du composé de bisamidrazone, pour 100 parties en poids de l'élastomère contenant du fluor.
  7. Composition élastomère contenant du fluor selon la revendication 1, dans laquelle on utilise environ 0,2 à environ 3 parties en poids du composé de bisamidrazone, pour 100 parties en poids de l'élastomère contenant du fluor.
EP96111051A 1995-07-13 1996-07-09 Composition d'élastomère contenant du fluor Expired - Lifetime EP0754721B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP200358/95 1995-07-13
JP20035895 1995-07-13
JP7200358A JP2891294B2 (ja) 1995-07-13 1995-07-13 含フッ素エラストマー組成物

Publications (3)

Publication Number Publication Date
EP0754721A2 EP0754721A2 (fr) 1997-01-22
EP0754721A3 EP0754721A3 (fr) 1997-03-26
EP0754721B1 true EP0754721B1 (fr) 2000-10-25

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EP96111051A Expired - Lifetime EP0754721B1 (fr) 1995-07-13 1996-07-09 Composition d'élastomère contenant du fluor

Country Status (5)

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US (1) US5637648A (fr)
EP (1) EP0754721B1 (fr)
JP (1) JP2891294B2 (fr)
CN (1) CN1100820C (fr)
DE (1) DE69610746T2 (fr)

Cited By (1)

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RU2596746C2 (ru) * 2014-10-27 2016-09-10 Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") Эластомерная композиция на основе сополимера тетрафторэтилена и перфторалкилвиниловых эфиров

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US6281296B1 (en) 1998-08-10 2001-08-28 Dupont Dow Elastomers L.L.C. Curable perfluoroelastomer composition
US6638999B2 (en) 2000-02-08 2003-10-28 Dupont Dow Elastomers Llc. Curable perfluoroelastomer composition
CA2421708A1 (fr) * 2000-09-18 2002-03-28 3M Innovative Properties Company Compositions de fluoropolymeres a teneur en imidate
US6794457B2 (en) 2001-04-30 2004-09-21 3M Innovative Properties Company Fluoropolymer curing system containing a nitrogen cure site monomer
KR100581307B1 (ko) * 2001-12-17 2006-05-22 다이킨 고교 가부시키가이샤 엘라스토머 성형품
EP1587784B1 (fr) 2003-01-29 2014-10-15 Greene, Tweed Of Delaware, Inc. Agents vulcanisants a base de bisaminophenyle, agents vulcanisants a base d'amidine et accelerateurs de durcissement pour compositions perfluoroelastomeres
RU2380384C2 (ru) * 2003-01-29 2010-01-27 Грин, Твид Оф Делавэр, Инк. Вулканизирующие агенты на основе бисаминофенила и вулканизирующие агенты и ускорители вулканизации на основе амидина для перфторэластомерных композиций
EP1699829A1 (fr) 2003-12-30 2006-09-13 3M Innovative Properties Company Procede de coagulation de fluoropolymeres et composition
US20050143529A1 (en) * 2003-12-30 2005-06-30 3M Innovative Properties Company Fluoropolymer compositions with nitrogen curing
US7514506B2 (en) * 2004-03-31 2009-04-07 Greene, Tweed Of Delaware, Inc. Fast curing fluoroelastomeric compositions, adhesive fluoroelastomeric compositions and methods for bonding fluoroelastomeric compositions
US7402630B2 (en) 2004-12-16 2008-07-22 3M Innovative Properties Company Curing compositions for fluoropolymers
US7300985B2 (en) * 2004-12-21 2007-11-27 3M Innovative Properties Company Fluoropolymers having pendant amidoxime or amidrazone structures
US7294677B2 (en) * 2005-08-25 2007-11-13 3M Innovative Properties Company Catalyst for making fluoroelastomer compositions and methods of using the same
CN101300301A (zh) * 2005-10-31 2008-11-05 大金工业株式会社 聚四氟乙烯的成型方法、聚四氟乙烯成型体、交联性聚四氟乙烯、聚四氟乙烯交联体粉末、树脂混合组合物和树脂混合成型体
RU2319717C1 (ru) * 2006-07-10 2008-03-20 Федеральное государственное унитарное предприятие "Научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" Композиция на основе сополимера тетрафторэтилена и перфторалкилвиниловых эфиров
JP4807784B2 (ja) * 2006-07-14 2011-11-02 信越化学工業株式会社 含フッ素硬化性組成物
JP5228913B2 (ja) * 2006-10-03 2013-07-03 ユニマテック株式会社 含フッ素エラストマー組成物
KR101684719B1 (ko) 2009-06-25 2016-12-08 쓰리엠 이노베이티브 프로퍼티즈 캄파니 플루오로중합체를 위한 경화 조성물
GB0917450D0 (en) 2009-10-06 2009-11-18 3M Innovative Properties Co Triazine containing fluoropolyether elastomers having very low glass transition temperatures, compositions containing them and methods of making them
US20120009438A1 (en) 2010-07-09 2012-01-12 3M Innovative Properties Company Triazine containing fluoroelastomers having low glass transition temperature
US9365712B2 (en) 2010-09-24 2016-06-14 Greene, Tweed Technologies, Inc. Fluorine-containing elastomer compositions suitable for high temperature applications
JP5833657B2 (ja) 2010-09-24 2015-12-16 グリーン， ツイード オブ デラウェア， インコーポレイテッド 高温への適用に適したフッ素含有エラストマー組成物
US9169339B2 (en) * 2010-12-07 2015-10-27 Daikin Industries, Ltd. Curable composition, molded product and method for producing molded product
US8765875B2 (en) 2011-03-31 2014-07-01 E I Du Pont De Nemours And Company Curable fluoroelastomer composition
US8618222B2 (en) 2011-03-31 2013-12-31 E I Du Pont De Nemours And Company Curable fluoroelastomer composition
US8338542B1 (en) 2012-06-25 2012-12-25 E I Du Pont De Nemours And Company Curable fluoroelastomer composition
US20130345365A1 (en) 2012-06-25 2013-12-26 E I Du Pont De Nemours And Company Curable fluoroelastomer composition
CN108473718B (zh) 2015-10-29 2021-03-30 纳幕尔杜邦公司 可固化的含氟弹性体组合物

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JPS59217749A (ja) * 1983-05-24 1984-12-07 Asahi Chem Ind Co Ltd 含フツ素エラストマ−組成物
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JP2850943B2 (ja) * 1994-10-21 1999-01-27 日本メクトロン株式会社 ビスアミドラゾン化合物よりなる含フッ素エラストマー用加硫剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2596746C2 (ru) * 2014-10-27 2016-09-10 Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") Эластомерная композиция на основе сополимера тетрафторэтилена и перфторалкилвиниловых эфиров

Also Published As

Publication number Publication date
DE69610746T2 (de) 2001-05-03
DE69610746D1 (de) 2000-11-30
US5637648A (en) 1997-06-10
JPH0931283A (ja) 1997-02-04
EP0754721A3 (fr) 1997-03-26
CN1100820C (zh) 2003-02-05
EP0754721A2 (fr) 1997-01-22
CN1140731A (zh) 1997-01-22
JP2891294B2 (ja) 1999-05-17

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